1. Field of the Invention
The present invention relates to an aqueous coating composition. More particularly, the present invention relates to an aqueous coating composition which can be suitably used for coating surfaces of wood, plastics, ceramics, metals, and the like, is safe due to absence of heavy metals, produces excellent gloss and fine external appearance when applied, and exhibits superior durability and water resistance which are represented by properties resistant black heel marks and anti-scuff properties. The aqueous coating composition is particularly useful as a floor coating material.
2. Description of Background Art
Responding to recent regulations which impose certain limitations on the content of volatile organic compounds in floor coating compositions, various aqueous coating compositions have been proposed. For example, Publication of Translation of International Patent Application (Toku-Hyo Hei No. 8-501577 (WO 94/07938) discloses an aqueous coating composition prepared from a dicarboxylic acid, a monocarboxylic acid which contains a metal sulfonate group (containing Cu, Fe, or the like as a heavy metal), glycol, an amino alcohol, and a poly-functional compound which contains 3 or more hydroxyl groups. Because these aqueous coating compositions which contain heavy metals exhibit excellent durability, they are widely used for coating floor materials and the like.
However, in response to an increased concern about environmental problems in recent years under which complete assurance for pollution-free and safe materials is required, aqueous compositions containing no heavy metals are desired as coating compositions for floor materials which inherently should not cause water pollution problems and the like if handled in a well-controlled manner.
Japanese Patent No. 2973060 discloses an aqueous coating composition which is free from heavy metals, but contains an aqueous dispersing material possessing a free carboxyl group which is obtained by emulsion polymerization of an ethylenically unsaturated monomer, an amino alcohol, and an acetic acid ester.
However, these aqueous coating compositions which do not contain heavy metals are intended mainly for coating floors in homes, and are not necessarily satisfactory for coating floors requiring superior durability such as floors in department stores. Specifically, floors of department stores, for example, are not only subjected to severe contact with the shoes of a great number of customers, especially high-heeled shoes for women, but are also required to exhibit a beautiful appearance.
The present invention has been achieved in view of these problems and has an objective of providing an aqueous coating composition which is safe due to absence of heavy metals, produces excellent gloss and has a fine external appearance when coated, exhibits superior durability and water resistance which are represented by properties resistant to black heel marks (hereinafter called xe2x80x9cblack heel mark resistancexe2x80x9d) and anti-scuff properties, and is particularly useful as a floor coating material.
As a result of extensive studies, the present inventors have found that the above object can be achieved by an aqueous coating composition comprising (A) an aqueous dispersing material which is a copolymer having a glass transition temperature (Tg) of 80xc2x0 C. or less which is obtained by the copolymerization a specific unsaturated carboxylic acid, (meth)acrylic acid alkyl ester, and other monomers and (B) a specific aminoalcohol compound in a specific proportion. This finding has led to the completion of the present invention.
Specifically, the present invention provides the following aqueous coating compositions.
An aqueous coating composition comprising (A) 100 parts by weight (solid basis) of an aqueous dispersing material which is a copolymer having a glass transition temperature (Tg) of 80xc2x0 C. or less which is obtained by the copolymerization of (a) 2-40 wt % of xcex1,xcex2-unsaturated carboxylic acid (monomer (a)), (b) 20-90 wt % of (meth)acrylic acid alkyl ester (monomer (b)), and (c) 0-78 wt % of monomers (monomer (c)) polymerizable with the monomer (a) and monomer (b), and (B) 0.1-100 parts by weight of a compound shown by the following formula (1),
R3xe2x88x92nNXnxe2x80x83xe2x80x83(1)
wherein R represents a hydrogen atom, an alkyl group having 1-12 carbon atoms, or an aminoalkyl group having 1-12 carbon atoms, X represents a hydroxyalkyl group having 1-10 carbon atoms, and n is an integer from 1-3, provided that two or more Rs, if present, may be either different or identical and two or more Xs, if present, may be either different or identical.
The aqueous coating composition described in (1) above, further comprising (C) an alkali metal compound in an amount of 0.05-40 parts by weight for 100 parts by weight (solid basis) of the component (A).
Other objects, features and advantages of the invention will hereinafter become more readily apparent from the following description.
The present invention will now described in more detail by way of embodiments.
The aqueous coating composition of the composition is characterized by comprising (A) an aqueous dispersing material which is a specific copolymer (hereinafter xe2x80x9ccomponent (A)xe2x80x9d) having a glass transition temperature (Tg) of 80xc2x0 C. or less and (B) the compound shown by the above formula (1) (hereinafter xe2x80x9ccomponent (B)xe2x80x9d).
Each component for the aqueous coating composition will now be described in more detail.
1. Component (A)
The component (A) used in the present invention is a copolymer obtained by the copolymerization of (a) 2-40 wt % of xcex1,xcex2-unsaturated carboxylic acid (hereinafter xe2x80x9cmonomer (a)xe2x80x9d), (b) 20-90 wt % of (meth)acrylic acid alkyl ester (hereinafter xe2x80x9cmonomer (b)xe2x80x9d), and (c) 0-78 wt % of monomers polymerizable with the monomer (a) and monomer (b), and (B) (hereinafter xe2x80x9cmonomer (c)xe2x80x9d).
(1) Monomer (a)
As examples of the monomer (a) used in the present invention, (meth)acrylic acid, fumaric acid, itaconic acid, monoalkyl itaconate, maleic acid, crotonic acid, 2-methacryloyloxyethlhexahydrophtalic acid, and the like can be given. Of these, (meth)acrylic acid is preferred in view of polymerization stability and durability.
These monomer (a) compounds can be used either individually or in combination of two or more.
The amount of the monomer (a) among all monomers is in the range of 2-40 wt %, preferably 5-35 wt %, and more preferably 10-30 wt %. If this amount is less than 2 wt %, the product exhibits only poor durability; if more than 40 wt %, leveling characteristics of the product are impaired.
(2) Monomer (b)
Given as examples of the monomer (b) used in the present invention are methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, i-propyl(meth)acrylate, n-butyl(meth)acrylate, i-butyl(meth)acrylate, n-amyl(meth)acrylate, i-amyl(meth)acrylate, hexyl(meth)acrylate, ethylhexyl(meth)acrylate, i-nonyl(meth)acrylate, decyl(meth)acrylate, hydroxymethyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxyamyl(meth)acrylate, hydroxyhexyl(meth)acrylate, cyclohexyl(meth)acrylate, and the like. Of these, butyl(meth)acrylate and methyl(meth)acrylate are preferred in view of durability and weather resistance.
These monomer (b) compounds can be used either individually or in combination of two or more.
The amount of monomer (b) among all the monomers is in the range of 30-90 wt %, preferably 40-80 wt %, and more preferably 50-70 wt %. If less than 30 wt %, the product has poor water resistance and weather resistance; if more than 90 wt %, glossiness is poor.
(3) Monomer (c)
The following compounds can be given as the monomer (c) compounds used in the present invention:
benzyl(meth)acrylate, phenoxyethyl(meth)acrylate, alkylphenoxyethyl(meth)acrylate, phenoxydiethylene glycol(meth)acrylate, phenoxypolyethylene glycol(meth)acrylate, alkylphenol ethylene oxide(meth)acrylate, alkylphenol propylene oxide(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, ethylene glycol(meth)acrylate monophthalate, and ethylene glycol(meth)acrylate hydroxyethyl phthalate;
polyester(meth)acrylates;
epoxy compounds such as allyl glycidyl ether, glycidyl(meth)acrylate, and methyl glycidyl(meth)acrylate; poly-functional monomers such as divinylbenzene, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate;
amide compounds such as (meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N,Nxe2x80x2-methylenebisacrylamide, diacetone acrylamide, maleic acid amide, and maleimide; vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl acetate, and fatty acid vinyl esters;
Fluorine-containing monomers such as trifluoroethyl(meth)acrylate and pentadecafluorooctyl(meth)acrylate; reactive silicone compounds such as xcex3-methacryloylpropanetrimethoxysilane and xcex1-(3-methacryloxypropyl)polydimethylsiloxane;
aromatic vinyl compounds such as styrene, xcex1-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-t-butylstyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 1-vinylnaphthalene, and divinylbenzene;
aminoalkyl esters of ethylene-based unsaturated carboxylic acid such as monoamines, aminoethyl acrylate, dimethylaminoethyl acrylate, and butylaminoethyl acrylate; aminoalkyl amides of ethylene-based unsaturated carboxylic acid such as aminoethyl acrylamide, dimethylaminomethyl methacrylamide, and methylaminopropyl methacrylamide; and cyanated vinyl monomers such as (meth)acrylonitrile and xcex1-chloroacrylonitrile;
aldo group-containing monomers such as acrolein, formyl styrene, formyl-xcex1-styrene, and (meth)acrylamide pivalinealdehyde;
keto group-containing monomers such as diacetone(meth)acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl n-propyl ketone, vinyl i-propyl ketone, vinyl n-butyl ketone, vinyl i-butyl ketone, vinyl sec-butyl ketone, and vinyl t-butyl ketone; and
acetoacetyl group-containing unsaturated monomers such as acetoacetoxy(meth)acrylate and allyl acetoacetoate.
Of these, aromatic vinyl monomers such as styrene and the like are preferred in view of superior gloss of the products.
These monomer (c) compounds can be used either individually or in combination of two or more.
Although the monomer (c) is not an essential component in the present invention, the content among all the monomers is in the range of 0-78 wt %, preferably 0.5-60 wt %, and more preferably 1-50 wt %. If more than 78 wt %, the resulting products exhibit poor durability.
(4) Method for Preparing the Component (A)
There is no specific restriction to the method for preparing the aqueous dispersing material which is the component (A) of the present invention. For example, the aqueous dispersing material can be obtained as an emulsion of the copolymer by a conventional emulsion polymerization method. More specifically, a mixture prepared by adding the above monomers, an emulsifying agent, an initiator, a reducing agent, a chain transfer agent, a chelating agent, a pH modifier, and the like to an aqueous medium is subjected to a polymerization reaction at 30-100xc2x0 C. for 1-30 hours to obtain an aqueous dispersing material.
Emulsifying agents which can be used in the above method include, but are not limited to, anionic emulsifying agents, nonionic emulsifying agents, combined anionic-nonionic emulsifying agents, amphoteric surfactants, cationic surfactants, reactive emulsifying agents which are copolymerizable with the above-described monomers, water soluble polymers, and the like.
As examples of anionic emulsifying agents, higher alcohol sodium sulfate, alkylbenzene sodium sulfonate, succinic acid dialkyl ester sodium sulfonate, alkyl diphenyl ether sodium disulfonate, sulphate of polyoxyethylene alkyl (or alkylphenyl) ether, and the like can be given. Of these, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sulphate of polyoxyethylene alkyl ether are preferred.
As examples of nonionic emulsifying agents, polyoxyethylene alkyl ether, polyoxyethylene alkylallyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, and the like can be given. Of these, polyoxyethylene alkyl ether is preferred.
As examples of amphoteric emulsifying agents, lauryl betaine and the like can be given.
As examples of cationic emulsifying agents, alkyl pyridinyl chloride, alkylammonium chloride, and the like can be given.
As examples of reactive emulsifying agents copolymerizable with the monomers, sodium styrene sulfonate, sodium allylalkyl sulfonate, alkyl allyl sulfosuccinate, polyoxyethylene alkylallyl glycerol ether sulfate, polyoxyethylene alkylphenol allyl glycerol ether sulfate, and the like can be given. Of these, sodium styrene sulfonatet, sodium allylalkyl sulfonate, alkyl allyl sulfosuccinate are preferred.
As water soluble polymers used as an emulsifying agent, polyvinyl alcohol, polyacrylate, water soluble (meth)acrylate copolymer, salt of styrene-maleic acid copolymer, poly(meth)acrylamide, copolymer of poly(meth)acrylamide, and the like can be given. Of these, partially saponified polyvinyl alcohol, water soluble (meth)acrylate copolymer, salts of carboxylated aromatic vinyl copolymer such as a salt of styrene-maleic acid copolymer, styrene-(meth)acrylic acid copolymer, and the like are preferred.
Of these emulsifying agents, soap-free type reactive emulsifying agents are preferred due to high hot water resistance.
The amount of emulsifying agent used is preferably 0-5 parts by weight for 100 parts by weight of the total amount of monomers.
If more than 5 parts by weight, the resulting product may have inferior water resistance.
As examples of polymerization initiators, water soluble initiators and the oil soluble initiators can be given.
Persulfates, hydrogen peroxides, and the like can be given as water soluble initiators. As required, these initiators can be used in combination with a reducing agent.
As examples of reducing agents, sodium pyro-bisulfite, sodium sulfite, sodium thiosulfate, L-ascorbic acid and a salt thereof, sodium formaldehyde sulfoxylate, and the like can be given.
As examples of oil soluble initiators, 2,2xe2x80x2-azobisisobutyronitrile, 2,2xe2x80x2-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2xe2x80x2-azobis-2,4-dimethylvaleronitrile, 1,1xe2x80x2-azobis-cyclohexane-1-nitrile, benzoyl peroxide, dibutyl peroxide, cumenehydroperoxide, and the like can be given. Of these, cumenehydroperoxide, isopropylbenzene hydroperoxide, p-methane hydroperoxide, azobisisobutyronitrile, benzoyl peroxide, t-butylhydroperoxide, 3,5,5-trimethylhexanol peroxide, t-butylperoxy(2-ethylhexanoate), and the like are preferred.
These polymerization initiators can be used dissolved either in monomers or a solvent.
The amount of polymerization initiator used is preferably from 0.1-3 parts by weight for 100 parts by weight of the total amount of monomers.
Given as examples of chain transfer agents are halogenated hydrocarbons (for example, carbon tetrachloride, chloroform, bromoform), mercaptans (for example, n-dodecylmercaptan, t-dodecylmercaptan, n-octylmercaptan), xanthogens (for example, dimethylxanthogen disulfide, diisopropylxanthogen disulfide), terpenes (for example, dipentene, terpinolene), 1,1-diphenylethylene, xcex1-methylstyrene dimers (at least one of 2,4-diphenyl-4-methyl-1-pentene (I), 2,4-diphenyl-4-methyl-pentene (II), and 1,1,3-trimethyl-3-phenylindan (III), and preferably a mixture of (I), (II), and (III) at a weight ratio (I)/((II)+(III))=(40xe2x88x92100)/(0xe2x88x9260)), unsaturated cyclic hydrocarbon compounds (for example, 9,10-dihydroanthracene, 1,4-dihydronaphthalene, indene, 1,4-cyclohexadiene), unsaturated heterocyclic compounds (for example, xanthene, 2,5-dihydrofuran), and the like.
The amount of chain transfer agent used is preferably from 0-5 parts by weight for 100 parts by weight of the total amount of monomers.
A solvent such as methyl ethyl ketone, acetone, trichlorotrifluoroethane, methyl isobutyl ketone, dimethylsulfoxide, toluene, dibutylphthalate, methylpyrrolidone, ethyl acetate, alcohols, cellosolves, carbinols, and the like can be used in the emulsion polymerization, as required.
To ensure excellent processability, protection against disasters, environmental safety, and manufacturing safety, the amount of these solvents used in the composition is preferably from 0-10 part by weight for 100 parts by weight of total amount of monomers.
The emulsion polymerization can be carried out by, for example, polymerizing all the monomers in one reaction, polymerizing part of the monomers first and then continuously or intermittently adding the remaining part of the monomers to polymerize, polymerizing the monomers while continuously adding monomers during polymerization. When seed polymerization is adopted, seed particles are prepared first by copolymerizing the monomers by emulsion polymerization, then adding the copolymers (a) to (c) to the seeds to perform emulsion polymerization.
The final polymerization conversion rate of the copolymer used in the present invention is from 90 to 100 wt %, and preferably from 95 to 100 wt %.
The weight average molecular weight of the copolymer used in the present invention is from 3,000 to 1,000,000, preferably from 10,000 to 800,000, and more preferably 30,000 to 500,000. If less than 3,000, durability of the products is inferior; if more than 1,000,000, leveling characteristics may be poor.
The glass transition temperature of the copolymer used in the present invention is preferably from 10-180xc2x0 C., and more preferably from 20-175xc2x0 C. If less than 10xc2x0 C., durability of the products is inferior; if more than 180xc2x0 C., film-forming capability may be poor.
The average particle diameter of the copolymer used in the present invention is preferably from 0.01 to 1 xcexcm, and more preferably from 0.02 to 0.5 xcexcm, and particularly preferably from 0.05 to 0.2 xcexcm. If more than 1 xcexcm, glossiness of the product may be inferior; if less than 0.01 xcexcm, leveling characteristics may be poor.
2. Component (B)
The component (B) which is used in the present invention is a compound shown by the above-described formula (1).
In the formula (1), the alkyl group represented by R has a carbon atom number from 1-12, and preferably from 1-4, and is, for example, a methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, n-hexyl group, or the like.
The aminoalkyl group represented by R has a carbon atom number from 1-12, and preferably from 1-4, and is, for example, an amino methyl, amino ethyl group, or the like. Two or more Rs, if present, may be either identical or different.
The hydroxy alkyl group represented by X has a carbon atom number from 1-10, and preferably from 1-4, and is, for example, xcex1-hydroxyethyl, xcex2-hydroxyethyl, xcex3-hydroxypropyl, and the like. Two or more Xs, if present, may be either identical or different.
As examples of the component (B) used in the present invention, xcex1-aminoalcohol, xcex2-aminoalcohol, diethanolamine, triethanolamine, 2-amino iso-hexyl alcohol, N,N-diethylethanolamine, N,N-dimethylethanolamine, aminoethylethanolamine, N-methyl-N,N-diethanolamine, N,N-dibutylethanolamine, N-methylethanolamine, 3-amino-1-propanol, and the like can be given. Of these, xcex2-aminoalcohol, diethanolamine, and triethanolamine are preferred in view of superior leveling characteristics and durability of the products.
These compounds may be used either individually or in combinations of two or more as the component (B).
The amount of the component (B), in terms of the amount of solid components, is in the range of 0.1-100 parts by weight, preferably 0.2-80 parts by weight, and more preferably 0.5-60 parts by weight, for 100 parts by weight of the component (A). If the amount of the component (B) is less than 0.1 part by weight, durability of the products is inferior; if more than 100 parts by weight, water resistance of the products is inferior.
3. Alkali Metal Compound (C)
In addition to the components (A) and (B), the aqueous coating composition of the present invention may comprise an alkali metal compound (C) (hereinafter xe2x80x9ccomponent (C)xe2x80x9d) in the amount from 0.05-40 parts by weight for 100 parts by weight (solid basis) of the component (A).
A hydroxide of alkali metal such as sodium hydroxide and potassium hydroxide, a carbonate of alkali metal such as sodium carbonate and potassium carbonate, a hydrogencarbonate of alkali metal such as sodium hydrogencarbonate, and the like can be given as examples of the component (C) used in the present invention. Among these, sodium hydroxide, potassium hydroxide, and the like are preferable.
4. Other Components
In addition to the above components (A) and (B), and the component (C) which is used as required, various components such as (D) a wax emulsion, (E) an alkali-soluble resin, (F) a film-forming adjuvant,(G) various other additives such as a wetting agent, dispersant, leveling agent, antiseptic agent, anti-foaming agent, and the like may be added to the aqueous coating composition of the present invention.
As the wax emulsion (D), a polyethylene-based emulsion and the like can be given. The amount of the component (D) on a solids basis is in the range of 0-40 parts by weight, preferably 5-30 parts by weight, and more preferably 10-30 parts by weight, for 100 parts by weight of the copolymer (A). If more than 40 parts by weight, the product has poor glossiness and inferior appearance.
As examples of an alkali-soluble resin (E), styrene-maleic acid copolymer resin, shellac, rosin-modified maleic resin, and the like can be given. These resins can improve the leveling characteristics and delamination characteristics of the aqueous coating composition. The amount of these resins on a solids basis is in the range of 0-50 parts by weight, preferably 5-40 parts by weight, and more preferably 10-30 parts by weight, for 100 parts by weight of the copolymer (A). If more than 50 parts by weight, the resulting product may have inferior durability.
Component (F) may be a film-forming adjuvant such as, for example, tributoxy phosphate, a polyhydric alcohol such as diethylene glycol, isophorone, benzyl alcohol, monoethyl monomethyl ether such as 3-methoxy butanol-1, benzylbutyl phthalate, dibutyl phthalate, dimethyl phthalate, triphenyl phosphate, and carbitol; or additives commonly used for coatings such as a pigment. The amount of the component (F) on a solids basis is in the range from 0-50 parts by weight, preferably 5-40 parts by weight, and more preferably 10-30 parts by weight, for 100 parts by weight of the copolymer (A). If more than 50 parts by weight, the resulting product may have inferior durability.
(G) Other Additives Such as a Wetting Agent, Dispersant, Leveling Agent, Antiseptic Agent, and Anti-foaming Agent
As examples of a wetting agent, potassium salt of the perfluoroalkyl carboxylic acid and the like can be given.
As examples of a dispersant, anionic surfactants, nonionic surfactanst, and the like can be given.
As examples of a leveling agent, rosin acid ester and the like can be given.
As examples of an antiseptic agent, a mixture of 2-methyl-4-iso-azophosphorus-3-one, 5-chloro-2-methyl-4-iso-azophosphorus-3-one, and the like can be given.
5. Glass Transition Temperature (Tg) of Copolymer
The aqueous coating composition of the present invention is characterized by a glass transition temperature (Tg) of 80xc2x0 C. of the copolymer.
If the glass transition temperature (Tg) of the copolymer is above 80xc2x0 C., durability becomes insufficient because the film-forming capability of the composition decreases. If less than 10xc2x0 C., durability may be inferior.
Glass transition temperature (Tg) for the compositions A, B, C, . . . in the present invention means a glass transition temperature (Tg) calculated by a FOX formula which is shown by the following formula (1):
1/Tg (K)=(weight fraction of A/TgA (K))+(weight fraction of B/TgB (K))+(weight fraction of C/TgC (K)) +xe2x80x83xe2x80x83(1)
The aqueous coating composition of the present invention is applied to a substrate by spraying, fabric coating, or brushing, immediately followed by drying in air or by heating, thereby producing a strong coating film.